Thermal transfer image-receiving sheet

Abstract: A thermal transfer image-receiving sheet comprising a substrate sheet (1), a dye-receptive layer (2) provided on one surface of the substrate sheet and a dye-unreceptive layer (3) provided on the other surface of the substrate sheet, the dye-unreceptive layer comprising a release agent which is the same as that contained in the dye-receptive layer or does not migrate to other places, for example, comprises an amino-modified silicone and an epoxy-modified silicone or a product of a reaction of both of them, or an addition-polymerizable silicone or a cured product obtained by a reaction thereof. A thermal transfer image-receiving sheet comprising a substrate sheet, a dye-receptive layer provided on one surface of the substrate sheet and a lubricious back surface layer provided on the other surface of the substrate sheet, the lubricious back surface layer being composed mainly of a binder and a nylon filler.

Description: The present invention relates to a thermal transfer image-receiving sheet which is receptive to a dye transferred from a thermal transfer sheet by heating, which thermal transfer image-receiving sheet can be widely utilized in the field of various color printers including video printers. In recent years, a system where video images, TV images and still images, such as computer graphics, are directly printed as a full color image has advanced, which has led to a rapid expansion of the market thereof. Among others, a system which has attracted attention is such that a sublimable dye as a recording material is put on an image-receiving sheet and heated by means of a thermal head in response to recording signals to transfer the dye onto the image-receiving sheet, thereby forming a recorded image. In this recording system, since a dye is used as the colorant, the sharpness is very high and, at the same time, the transparency is excellent, so that it is possible to provide an image having excellent reproduction and gradation of intermediate colors equivalent to those of an image formed by the conventional full color offset printing and gravure printing. In this case, the formed image has a high quality comparable to photographic images. Printers in current use in the above thermal transfer system are mainly of such a type that a thermal transfer image-receiving sheet is automatically carried to a thermal transfer section within a printer and, after printing, automatically delivered from the printer. Further, in order to carry out overlap printing of three colors or four colors, it is a common practice to provide a detection mark on the thermal transfer image-receiving sheet in its image-unreceptive surface, that is, the back surface, located opposite to the image-receiving surface for the purpose of preventing the occurrence of a shear in the printing position of each color. Not only the construction of the thermal transfer sheet but also the construction of the image-receiving sheet on which an image is to be formed is important to the practice of the above thermal transfer method with a high efficiency. In particular, the properties of the image-unreceptive surface (back surface) located opposite to the image-receptive surface of the thermal transfer image-receiving sheet are important for smoothly carrying out automatic feed and delivery of the thermal transfer image-receiving sheet. For example, when the image-receiving sheets with an image being formed thereon are put on top of another for storage, the dye on the print surface migrates to the back surface of another thermal transfer image-receiving sheet in contact with the print surface to remarkably stain the back surface, which deteriorates the appearance. Further, in this case, the color of the print surface is partly or entirely dropped out, or restaining occur. Furthermore, in domestic use, a back surface free from a detection mark as in photographic paper is preferred from the viewpoint of appearance. However, when no detection mark is provided, it is difficult to distinguish the image-receptive layer from the back surface. When the thermal transfer image-receiving sheet is set in a printer in such a state that the image-receiving surface and the back surface are inversive, the erroneous setting cannot be detected by the printer and the printer begins to print. If that happens, in the conventional thermal transfer image-receiving sheet, fusing between the thermal transfer sheet and the back surface of the thermal transfer image-receiving sheet occurs within the printer, which inhibits the thermal transfer image-receiving sheet from being delivered from the printer, so that the printer should be sent to a maker for repair. The provision of a dye-receptive layer on both surfaces of the substrate sheet is considered as a means for solving the problem of heat fusing of the back surface. In this case, however, when prints are put on top of one another for storage, the dye migrates to cause problems of a lowering in image density, staining of contact surface, restaining and the like. Furthermore, since the dye-receptive layer comprises a dyeable resin and is even, the image-receptive layers are likely to come into close contact with each other, which, also in the stage before printing, results in a problem of a failure in automatic feed such as a problem that a plurality of image-receiving sheets are carried together in an overlapped state in a feeder of a printer. For example, even though a filler is added to the image-receptive layer for the purpose of preventing the occurrence of this problem, the highlight portion of the print is likely to become unsharp. Another means for solving the above problem is to add a release agent to the back surface layer as a dye-unreceptive layer. However, if the release agent is added in an amount sufficient to impart satisfactory releasability, the releasing component contained in the back surface layer is transferred to the image-receptive surface when the back surface layer is put on top of the image-receptive surface, which unfavorably raises problems of occurrence of a failure in printing such as partial dropout in the print portion and uneven print density, a lowering in coefficient of dynamic friction between the image-receptive surface of the image-receiving sheet and the transfer agent surface of the thermal transfer sheet, which is causative of the occurrence of a shear in the printing position of each color. Further, in this case, the releasing component contained in the back surface layer migrates to a feed and delivery mechanism, such as a paper feed rubber roller, and a platen rubber roller in a printer, which gives rise to a change in coefficient of friction of these members, so that troubles are likely to occur such 5 as a failure in feed and delivery of sheets and oblique carrying of the image-receiving sheet. EP-A-0 409 526 discloses a receiver sheet having an antistatic back-coat layer comprising inert particulate fillers embedded in the cross-linked product of a thermoplastic vinyl polymer having terminal reactive hydroxyl groups. EP-A-0 541 266 discloses a thermal transfer receiver sheet having a back-coat comprising a cross-linked polymer matrix. EP-A-0 545 710 discloses a thermal transfer dye image-receiving sheet having a back-surface coating layer comprising silicone block copolymer resins, silicone oils, silicone varnishes, fluorine compounds, phosphate ester compounds or fatty acid ester compounds. WO-A-94/29116 describes dye donor sheets having a heat-resistant back-coat layer. EP-A-0 234. 563 discloses a heat transferable sheet having an anti-static back-coat layer comprising a surfactant as an antistatic agent. EP-A-0 194 106 discloses a heat-transfer sheet having a lubricating layer on the back surface thereof. Accordingly, an object of the present invention is to solve the above problems of the prior art and to provide a thermal transfer image-receiving sheet having excellent service properties for use in a thermal transfer system where a sublimable dye is used, which thermal transfer image-receiving sheet hardly causes a lowering in print density and migration of dye to the back surface of the image-receiving sheet when a plurality of image-receiving sheets are put on top of another for storage, can be delivered from the printer without fusing to the thermal transfer sheet by virtue of excellent releasability of the back surface even though printing is carried out on the thermal transfer image-receiving sheet with the image-receiving surface and the back surface being inversive and is free from an adverse effect of the release agent added to the back surface layer on the image-receiving surface and substantially free from the migration of the release agent to a sheet feed and delivery mechanism and a platen rubber roller. The present inventors have made extensive and intensive studies with a view to solving the above problems, which has led to the completion of the present invention. According to the present invention, there is provided a thermal transfer image-receiving sheet comprising a substrate sheet, a dye-receptive layer provided on one surface of said substrate sheet and a lubricious back surface layer provided on the other surface of said substrate sheet, said lubricious back surface layer being composed mainly of a binder and a nylon 12 filler. Fig. 1 is a cross-sectional view of an embodiment of the thermal transfer image-receiving sheet according to the present invention; Fig. 2 is a schematic view of the essential part showing the measurement of coefficient of friction between the image-receiving surface and the back surface of thermal transfer image-receiving sheets; and Fig. 3 is a schematic view showing the measurement of coefficient of friction between the back surface of a thermal transfer image-receiving sheet and a rubber roll for the feed and delivery of sheets in a printer: Preferred embodiments of the present invention will now be described in more detail with reference to the accompanying drawings. Embodiments of the present invention will now be described in more detail with reference to the accompanying drawings. A typical cross-sectional view of an embodiment of the thermal transfer image-receiving sheet according to the present invention is shown in Fig. 1. This thermal transfer image-receiving sheet comprises a substrate sheet 1, a dye-receptive layer 2 provided on one surface of the substrate sheet and a lubricious back surface layer 30 provided on the other surface of the substrate sheet, characterized in that the lubricious back surface layer 30 is composed mainly of a binder and a nylon filler. Materials for constituting each layer of the thermal transfer image-receiving sheet of the present invention will now be described. 1) Substrate sheet In the present invention, materials usable in the substrate sheet include papers. Any of various papers per se, converted papers and other types of papers may be used, and examples thereof include wood free paper, coated paper, art paper, cast coated paper and fiber board and other types of papers such as paper impregnated with an resin emulsion, a synthetic rubber latex or the like and paper containing an internally added synthetic resin. Further, a laminated paper comprising the above paper and various plastic films. When synthetic paper is used, polystyrene synthetic paper, polyolefin synthetic paper and the like are suitable. Examples of the plastic film include a polyolefin resin film, a polyvinyl chloride film, a polyester resin film, a polystyrene film, a polycarbonate film, a polyacrylonitrile film and a polymethacrylate film. These plastic films are not particularly limited, and use may be made of not only transparent films but also a white opaque film or a foamed film prepared by adding a white pigment or filler to the above synthetic resin and forming a film from the mixture or expanding the mixture. When plastic films are used, plasticizers and other additives may be optionally added for the purpose of regulating the rigidity of the films. The above materials may be used alone. Alternatively, as described above in connection with paper, they may be used as a laminate comprising a combination thereof with other materials. Further, in the formation of a dye-receptive layer or a lubricious back surface layer on the above substrate sheet, it is also possible to conduct a corona discharge treatment or provide a primer coating or an intermediate layer according to need. The thickness of the substrate sheet is in the range of from about 10 µm to 400 µm, preferably in the range of from about 100 µm to 300 µm. When the image-receiving sheet is used in applications where an translucent image is required, such as OHP sheets, a transparent polyethylene terephthalate sheet having a thickness of about 50 to 200 µm is suitable. 2) Dye-receptive layer In the thermal transfer image-receiving sheet of the present invention, the dye-receptive layer is not particularly limited and may be any known dye-receptive layer commonly used in the sublimation thermal dye transfer system. For example, the following materials may be used. (i) Resins having an ester bond Polyester resins, polyacrylic ester resins, polycarbonate resins, polyvinyl acetate resins, styrene acrylate resins, vinyltoluene acrylate resins and the like. (ii) Resins having a urethane bond Polyurethane resins and the like. (iii) Resins having an amide bond Polyamide resins and the like. (iv) Resins having a urea bond Urea resins and the like. (v) Other resins having a high polarity Polycaprolactone resins, styrene/maleic anhydride resins, polyvinyl chloride resins, polyacrylonitrile resins and the like. In addition to the above synthetic resins, mixtures or copolymers thereof may also be used. In the thermal transfer, the dye-receptive layer is brought in contact with a thermal transfer sheet, and the laminate is pressed with heating by means of a thermal head or the like, so that the dye-receptive layer is likely to stick to the surface of the thermal transfer sheet. For this reason, in the formation of the dye-receptive layer, a releasing agent permeable to a dye is generally incorporated into the above resin. Solid waxes, fluorine or phosphoric ester surfactants, silicone oils may be used as the release agent. Although the silicone oils may be in an oil form, reaction-curable silicone oils may be preferred. For example, a combination of an amino-modified silicone with an epoxy-modified silicone is preferred. The amount of the release agent added is 5 to 50% by weight, preferably 10 to 20% by weight, based on the weight of the resin when the release agent is solid wax, and 0.5 to 10% by weight based on the resin when the release agent is a fluorine or phosphoric ester surfactant. The curable silicone oils may be used in a large amount because they are not sticky, and the amount of the curable silicone oils added may be in the range of from 0.5 to 30% by weight. In all the above release agents, when the amount is excessively small, the releasing effect becomes unsatisfactory. On the other hand, when the amount is excessive, the receptivity to a dye is lowered, so that insufficient recording density and other adverse effects occur. Regarding the method for imparting the releasability to the dye-receptive layer, besides the above-described incorporation of a release agent into the dye-receptive layer, it is also possible to separately provide a release layer on the dye-receptive layer. Further, if necessary, the dye-receptive layer may contain inorganic fillers, such as finely divided silica and titanium oxide, antioxidants and ultraviolet absorbers. The dye-receptive layer may be formed on the substrate sheet, for example, by coating the substrate sheet with a suitable organic solvent solution or water or organic solvent dispersion of above materials by gravure printing, screen printing or reverse roll coating using a gravure print or die coating and drying the resultant coating. For some materials, it is possible to form the dye-receptive layer by melt extrusion coating without use of any organic solvent and water. Although the dye-receptive layer thus formed may have any desired thickness, the thickness is generally in the range of from 1 to 50 µm. 3) Lubricious back surface layer The thermal transfer image-receiving sheet of the present invention is mainly characterized by the lubricious back surface layer. The lubricious back surface layer serves to prevent the image-receiving sheet from curling at the time of thermal transfer from the thermal head by heat, to improve the antiblocking resistance and lubricity in such a state that a plurality of thermal transfer image-receiving sheets are put on top of one another, and to prevent the staining of the back surface of the image-receiving sheet caused by migration of a dye of the print during storage of image-receiving sheets after printing with the print surface facing the back surface. For attaining the above effects, the lubricious back surface layer is composed mainly of a resin having a low dyeability with a dye as a binder and a nylon filler incorporated into the binder. Specific examples of the above binder, that is, a resin having a low dyeability with a dye include acrylic resins, polystyrene resins, polyolefin resins, polyamide resins, polyvinyl butyral, polyvinyl alcohol and cellulose acetate resins. In addition, curing resins obtained by curing polyvinyl butyral, melamine, cellulose, acrylic resins and other resins by using a chelate, an isocyanate, irradiation with a radiation and other means are also preferred. The above examples of the resin are illustrative only, and the binder is not limited to the above resins only. Specifically, various other resins may be used so far as they have a low dyeability with a dye, and the resins may be used in the form of a mixture of two or more. The nylon filler is preferably one which has a molecular weight of 100,000 to 900,000, is spherical and has an average particle diameter of 0.01 to 30 µm, particularly preferably one which has a molecular weight of 100,000 to 500,000 and an average particle diameter of 0.01 to 10 µm. Regarding the kind of nylon fillers, nylon 12 filler is used because it has superior water resistance and gives rise to no change in properties upon water absorption. The nylon filler has a high melting point and good heat stability, oil resistance, chemical resistance and other properties and, therefore, is less likely to be dyed with a dye. Further, it has a self-lubricity and a low coefficient of friction and, when it has a molecular weight of 100,000 to 900,000, is hardly abraded and does not damage counter materials. The average particle diameter is preferably in the range of from 0.1 to 30 µm in the case of a thermal transfer image-receiving sheet for a reflection image and in the range of from 0.01 to 1 µm for a thermal transfer image-receiving sheet for a transparency image. When the particle diameter is excessively small, the filler is buried in the lubricious back surface layer, so that the function of lubricity is unsatisfactory. On the other hand, when the particle diameter is excessively large, the protrusion of the filler from the lubricious back surface layer becomes large, which unfavorably enhances the coefficient of friction and causes falling of the filler. The proportion of the nylon filler incorporated into the binder is preferably in the range of from 0.01 to 200% by weight. It is still preferably in the range of from 1 to 100% by weight in the case of a thermal transfer image-receiving sheet for a reflection image and in the range of from 0.05 to 2% by weight in the case of a thermal transfer image-receiving sheet for a transparency image. When the proportion of the nylon filler incorporated is less than 0.01% by weight, the lubricity is unsatisfactory, so that clogging of the sheet and other unfavorable phenomena occur. On the other hand, when it exceeds 200% by weight, the lubricity is so high that a shear in the printing position of colors and other unfavorable phenomena unfavorably occur. The lubricious back surface layer may be generally formed by coating a suitable organic solvent solution or water or organic solvent dispersion of the binder resin containing a nylon filler in the above-described suitable amount range and optional additives by a gravure printing method, a screen printing method, a reverse roll coating method using a gravure print or a die coating method and drying the resultant coating. For some materials, it is also possible to form the lubricious back surface layer by melt extrusion coating without use of any solvent and dispersion medium. The thickness of the lubricious back surface layer is generally in the range of from 1 to 70 µm. In the thermal transfer using the above-described thermal transfer image-receiving sheet according to the present invention, the thermal transfer sheet used, for example, comprises paper or a polyester film and, provided thereon, a dye transfer layer containing a sublimable dye and, optionally provided on the back surface of the paper or polyester film, a heat-resistance layer, and any conventional thermal transfer sheet, as such, may be used in the present invention. Also for a device used in the thermal transfer, any conventional device may be used. For example, a desired object can be sufficiently attained by applying a thermal energy of about 5 to 100 mJ/mm 2 through the control of a recording time by means of a thermal printer (for example, a video printer VY-100 manufactured by Hitachi, Limited). The thermal transfer image-receiving sheet according to the present invention comprises a substrate sheet, a dye-receptive layer provided on one surface of the substrate sheet and a lubricious back surface layer provided on the other surface of the substrate sheet, the lubricious back surface layer being composed mainly of a binder and a nylon 12 filler. By virtue of the above construction, the surface of the lubricious back surface layer of the image-receiving sheet is finely uneven, which contributes to an improvement in lubricity and blocking resistance, so that troubles in a printer can be eliminated such as feed of a plurality of sheets in an overlapped state and other troubles during carrying such as in automatic feed and delivery. Further, since the nylon filler has a high melting point and a self-lubricity and excellent oil and chemical resistance, even though the temperature of the image-receiving sheet is raised within a printer, the lubricity and the blocking resistance are not deteriorated, so that stable properties can be obtained. Furthermore, even when a plurality of image-receiving sheets are put on top of one another with the surface of the print facing the back surface and, in this state, are stored, staining of the back surface of the image-receiving sheet with a sublimable dye hardly occurs. In the thermal transfer image-receiving sheet according to the present invention, the nylon filler added to the back surface layer is a nylon 12 filler. The nylon 12 filler is superior to nylon 6 and nylon 66 in water resistance and less likely to absorb water, so that under high-humidity conditions it gives rise to no change in properties and can stably exhibit the above properties. Further, in the thermal transfer image-receiving sheet according to the present invention, the nylon filler may be spherical and have a molecular weight in the range of from 100,000 to 900,000. This embodiment contributes to a further improvement in lubricity and blocking resistance of the back surface of the image-receiving sheet and an improvement in abrasion resistance of the filler. Therefore, there is no possibility that powder generated by abrasion is transferred to the rubber roller and the like and damages the rubber roller and other counter materials, which contributes to a further improvement in stability. Furthermore, in the thermal transfer image-receiving sheet according to the present invention, the nylon filler may have an average particle diameter in the range of from 0.01 to 30 µm. This embodiment prevents the nylon filler being buried in the back surface layer or prevents excessive protrusion of the nylon filler from the back surface layer which enhances the coefficient of friction or causes falling of the filler, so that the contemplated properties on an effective level can be stably attained. Furthermore, in the thermal transfer image-receiving sheet according to the present invention, the binder of the lubricious back surface layer may be a resin undyable with a sublimable dye. According to this embodiment, the resistance to stain with a sublimable dye can be further improved, and stain of the back surface of the image-receiving sheet with a sublimable dye hardly occurs even when the image-receiving sheets after printing are put on top of one another in such a manner that the surface with an image being formed thereon faced the back surface, and, in this state, are stored. Example C1 Synthetic paper (Yupo FPG#150 having a thickness of 150 µm; manufactured by Oji-Yuka Synthetic Paper Co., Ltd.) was used as a substrate sheet, and a coating solution having the following composition for a dye-receptive layer was coated by means of a bar coater on one surface of the synthetic paper so that the coverage on a dry basis was 5.0 g/m 2 , and the resultant coating was dried. Subsequently, a coating solution having the following composition for a primer layer and a coating solution having the following composition for a lubricious back surface layer were successively coated on the other surface of the synthetic paper respectively at coverages on a dry basis of 0.2 g/m 2 and 1.0 g/m 2 by means of a bar coater, and, after each coating, the resultant coating was dried, thereby preparing a thermal transfer image-receiving sheet of Example C1. Composition of coating solution for dye-receptive layer Polyester resin (Vylon 600 manufactured by Toyobo Co., Ltd.) 40 parts by weight Vinyl chloride/vinyl acetate copolymer (#1000A manufactured by Denki Kagaku Kogyo K.K) 60 parts by weight Addition-polymerizable silicone (X-62-1212 manufactured by The Shin-Etsu Chemical Co., Ltd.) 10 parts by weight Catalyst (PL50T manufactured by The Shin-Etsu Chemical Co., Ltd.) 5 parts by weight Solvent (methyl ethyl ketone/ toluene; weight ratio = 1 : 1) 885 parts by weight Methyl ethyl ketone will be hereinafter referred to as "MEK." Composition of coating solution for primer layer Urethane resin (Nippollan 5199 manufactured by Nippon Polyurethane Industry Co., Ltd.) 25 parts by weight Solvent (isopropyl alcohol /toluene/MEK; weight ratio = 1 : 2 : 2) 75 parts by weight Isopropyl alcohol will be hereinafter referred to as "IPA." Composition of coating solution for lubricious back surface layer Acrylic resin (BR85 manufactured by Mitsubishi Rayon Co.,) 10 parts by weight Nylon 12 filler (MW330 manufactured by Shinto Paint Co., Ltd.) 2 parts by weight Solvent (MEK/toluene; weight ratio = 1 : 1) 88 parts by weight Example C2 A thermal transfer image-receiving sheet of Example C2 was prepared in the same manner as in Example C1, except that the coating solution for a lubricious back surface layer had the following composition. Composition of coating solution for lubricious back surface layer Acrylic resin (BR80 manufactured by Mitsubishi Rayon Co.,) 10 parts by weight Nylon 12 filler (MW330 manufactured by Shinto Paint Co., Ltd.) 2 parts by weight Solvent (MEK/toluene; weight ratio = 1 : 1) 88 parts by weight Example C3 A thermal transfer image-receiving sheet of Example C3 was prepared in the same manner as in Example C1, except that the coating solution for a lubricious back surface layer had the following composition. Composition of coating solution for lubricious back surface layer Acrylic resin (BR113 manufactured by Mitsubishi Rayon Co., Ltd.) 10 parts by weight Nylon 12 filler (MW330 manufactured by Shinto Paint Co., Ltd.) 2 parts by weight Solvent (MEK/toluene; weight ratio 88 parts by weight Example C4 A thermal transfer image-receiving sheet of Example C4 was prepared in the same manner as in Example C1, except that the coating solution for a primer layer and the coating solution for a lubricious back surface layer had the following respective compositions. Composition of coating solution for primer layer Polyolefin resin (Unistole R300 manufactured by Mitsui Petrochemical Industries, Ltd.) 35 parts by weight Solvent (toluene) 65 parts by weight Composition of coating solution for lubricious back surface layer Amorphous polyolefin resin (Zeonex 480 manufactured by Nippon Zeon Co., Ltd.) 10 parts by weight Nylon 12 filler (MW330 manufactured by Shinto Paint Co., Ltd.) 2 parts by weight Solvent (toluene) 88 parts by weight Example C5 A thermal transfer image-receiving sheet of Example C5 was prepared in the same manner as in Example C1, except that the coating of the primer layer was omitted and the coating solution for a lubricious back surface layer had the following composition. Composition of coating solution for lubricious back surface layer Polyvinyl butyral resin (3000-1 manufactured by Denki Kagaku Kogyo K.K) 10.0 parts by weight Chelate agent (Tenkarate TP110) 4.3 parts by weight Nylon 12 filler (MW330 manufactured by Shinto Paint Co., Ltd.) 2 parts by weight Solvent (MEK/toluene; weight ratio = 1 : 1) 83.7 parts by weight Example C6 A thermal transfer image-receiving sheet of Example C6 was prepared in the same manner as in Example C1, except that the coating of the primer layer was omitted and the coating solution for a lubricious back surface layer had the following composition. Composition of coating solution for lubricious back surface layer Melamine resin (Cymel 303 manufactured by Mitui-Cyanamid, Ltd.) 10 parts by weight Catalyst (Catalyst 6000 manufactured by Mitsui Toatsu Chemicals, Inc.) 5 parts by weight Nylon 12 filler (MW330 manufactured by Shinto Paint Co., Ltd.) 2 parts by weight Solvent (MEK/toluene; weight ratio = 1 : 1) 83 parts by weight Example C7 A thermal transfer image-receiving sheet of Example C7 was prepared in the same manner as in Example C1, except that a nylon 6 filler was used as the filler added to the coating solution for a lubricious back surface layer instead of the nylon 12 filler. The construction of comparative thermal transfer image-receiving sheets will now be described. Thermal transfer image-receiving sheets of Comparative Examples C1 to C7 were prepared in the same manner as in Example C1, except that the coating solution for a lubricious back surface layer was prepared by using the following fillers instead of the nylon 12 filler. (Comparative Example C1) A thermal transfer image-receiving sheet prepared by using polyethylene wax (particle diameter: 10 µm) instead of the nylon 12 filler. (Comparative Example C2) A thermal transfer image-receiving sheet prepared by using teflon powder (particle diameter: 0.5 µm) instead of the nylon 12 filler. (Comparative Example C3) A thermal transfer image-receiving sheet prepared by using talc (particle diameter: 1.8 µm) instead of the nylon 12 filler. (Comparative Example C4) A thermal transfer image-receiving sheet prepared by using clay (particle diameter: 0.4 µm) instead of the nylon 12 filler. (Comparative Example C5) A thermal transfer image-receiving sheet prepared by using acrylic beads (particle diameter: 10 µm) instead of the nylon 12 filler. (Comparative Example C6) A thermal transfer image-receiving sheet prepared by using ethylenebisamide instead of the nylon 12 filler. (Comparative Example C7) A thermal transfer image-receiving sheet prepared by using silicone powder (particle diameter: 1.5 µm) instead of the nylon 12 filler. (Tests and results) The thermal transfer image-receiving sheets of Examples C1 to C7 and Comparative Examples C1 to C7 thus prepared subjected to tests for the following items, and the results are given in Tables C1 and C2. 1) Coefficient of friction between image-receiving surface and back surface of image-receiving sheet (lubricity) The measurement of coefficient of friction between the image-receiving surface and the back surface of the image-receiving sheet was made with a tensile strength tester (Tensilon UCT100 manufactured by Orientec Co. Ltd.) by a method shown in Fig. 2. The coefficient of friction was expressed as a value obtained by dividing the measured value (g) by the load 2000 g of the weight. 2) Coefficient of friction between back surface of image-receiving sheet and rubber roll of printer for feeding paper In a device as shown in Fig.3, a rubber roll was rotated at a surface velocity of 6 cm/sec under a load of 300 g, and, 15 sec after the initiation of the rotation, the scale (g) of a spring balance was read. The measured value was divided by the load to determine the coefficient of friction of the back surface of the image-receiving sheet. 3) Dye offset resistance of back surface of image-receiving sheet A gradation pattern was printed on each thermal transfer image-receiving sheet by utilizing a transfer sheet using a cyan dye by means of a thermal dye sublimation transfer printer (VY-50 manufactured by Hitachi, Ltd.). The printed sheet was used as a sample, and the sample was cut into a size of 14 x 4 cm. The cut sheets were put on top of another in such a manner that the surface with an image being formed thereon faced the back surface. A smooth aluminum plate was put on each of the uppermost sheet and the lowermost sheet to sandwich the sheets between the aluminum plates. A load of 1.5 kg was applied to the assembly from the top thereof. In this state, the assembly was allowed to stand in a constant-temperature oven at 50°C for 7 days. Thereafter, the cut sheet samples were taken out of the oven, and the maximum color density of the back surface of the sheet sample was measured by a Macbeth color densitometer. Sample Filler/resin (filler particle diameter) Coefficient of friction between image-receiving surface and back surface of image-receiving sheet Coefficient of friction between back surface of image-receiving sheet and rubber roll Offset resistance Ex. C1 Nylon 12/BR85 (5-8 µm) 0.28 1.30 0.01 Ex. C2 Nylon 12/BR80 (5-8 µm) 0.33 1.09 0.01 Ex. C3 Nylon 12/BR113 (5-8 µm) - - 0.01 Ex. C4 Nylon 12/Zeonex 480 (5-8 µm) 0.30 1.09 0.01 Ex. C5 Nylon 12/PVB 3000-1 (5-8 µm) 0.18 1.30 0.01 Ex. C6 Nylon 12/Cymel 303 (5-8 µm) - - 0.01 Ex. C7 Nylon 6/BR85 0.30 1.09 0.02 Sample Filler/resin (filler particle diameter) Coefficient of friction between image-receiving surface and back surface of image-receiving sheet Coefficient of friction between back surface of image-receiving sheet and rubber roll Offset resistance Comp. Ex. C1 PE wax/BR85 (10 µm) 0.36 0.88 0.07 Comp. Ex. C2 Teflon powder/BR85 (0.5 µm) 0.41 0.88 0.03 Comp. Ex. C3 Talc/BR85 (1.8 µm) 0.37 0.94 0.06 Comp. Ex. C4 Clay/BR85 (0.4 µm) 0.48 0.17 0.05 Comp. Ex. C5 Acrylic bead/BR85 (10 µm) 0.49 0.17 0.07 Comp. Ex. C6 Ethylenebisamide/BR85 0.29 1.09 0.03 Comp. Ex. C7 Silicone powder/BR85 (1.5 µm) 0.41 0.94 0.07 (Evaluation of measured values) 1) The lower the coefficient of friction between the image-receiving surface and the back surface of the image-receiving sheet, the better the results. 2) The higher the coefficient of friction between the back surface of the image-receiving sheet and the rubber roll of the printer for feeding paper, the better the results. 3) The lower the numerical value for expressing the dye offset resistance of the back surface of the image-receiving sheet, the better the results. Apart from the above tests, in order to evaluate the feedability, deliverability and carriability of the image-receiving sheets under a high-temperature and high-humidity environment, a printing test on samples of Example C1 (nylon 12 filler used) and Example 7 (nylon 6 filler used) was made where printing was carried out on 50 sheets of sample in a continuos manner by means of a thermal dye sublimation transfer printer (VY-50) under an environment of 35°C and 80%RH. As a result, no failure occurred for the image-receiving sheet of Example C1, whereas a failure of the image-receiving sheet to be fed occurred for two sheets of the image-receiving sheet sample of Example C7. This indicates that the nylon 12 filler can maintain the effect even under high-temperature and high-humidity environments. The thermal transfer image-receiving sheet according to the present invention comprises a substrate sheet, a dye-receptive layer provided on one surface of the substrate sheet and a lubricious back surface layer provided on the other surface of the substrate sheet, the lubricious back surface layer being composed mainly of a binder and a nylon 12 filler. By virtue of the above construction, the surface of the lubricious back surface layer of the image-receiving sheet is finely uneven, which contributes to an improvement in lubricity and blocking resistance. Further, the nylon filler has a high melting point, a self-lubricity and excellent oil and chemical resistance. By virtue of these properties, troubles in a printer can be eliminated such as feed of a plurality of sheets in an overlapped state and other troubles during carrying such as in automatic feed and delivery. Furthermore, even though the temperature of the image-receiving sheet is raised within a printer, the lubricity and the blocking resistance are not deteriorated, so that stable properties can be obtained. Furthermore, even when a plurality of image-receiving sheets are put on top of one another with the surface of the print facing the back surface and, in this state, are stored, the offset of the sublimable dye onto the back surface of the image-receiving sheet can be prevented. Thus, according to the present invention, a thermal transfer-image receiving sheet having the above excellent properties can be provided. In the thermal transfer image-receiving sheet according to the present invention, the nylon filler added to the back surface layer is a nylon 12 filler. The nylon 12 filler is superior to nylon 6 and nylon 66 in water resistance and less likely to absorb water, so that under high-temperature and high-humidity conditions it gives rise to no change in properties and can stably exhibit the above properties. Further, in the thermal transfer image-receiving sheet according to the present invention, the nylon filler may be spherical and have a molecular weight in the range of from 100,000 to 900,000. This embodiment contributes to a further improvement in lubricity and blocking resistance of the back surface of the image-receiving sheet and an improvement in abrasion resistance of the filler. Therefore, there is no possibility that powder generated by abrasion is adhered to the rubber roller and the like and damages the rubber roller and other counter materials. Furthermore, in the thermal transfer image-receiving sheet according to the present invention, the nylon filler may have an average particle diameter in the range of from 0.01 to 30 µm. This embodiment prevents the nylon filler from being buried in the back surface layer or prevents excessive protrusion of the nylon filler from the back surface layer which enhances the coefficient of friction or causes falling of the filler, so that the contemplated properties can be stably attained. Furthermore, in the thermal transfer image-receiving sheet according to the present invention, the binder may be a resin undyeable with a sublimable dye. According to this embodiment in combination with the uneven back surface, the resistance to stain with a sublimable dye can be further improved, and the offset of a sublimable dye hardly occurs even when the image-receiving sheets after printing are put on top of one another in such a manner that the surface with an image being formed thereon faced the back surface, and, in this state, are stored.

Claims: A thermal transfer image-receiving sheet comprising a substrate sheet, a dye-receptive layer provided on one surface of said substrate sheet and a lubricious back surface layer being provided on the other surface of the substrate sheet, said lubricious back surface layer being composed mainly of a binder and a nylon 12 filler. The thermal transfer image-receiving sheet according to claim 1 wherein said nylon filler is spherical and has a molecular weight in the range of from 100,000 to 900,000. The thermal transfer image-receiving sheet according to claim 1 or 2, wherein said nylon filler has an average particle diameter in the range of from 0.01 to 30 µm. The thermal transfer image-receiving sheet according to claim 1, 2 or 3 wherein said binder is a resin undyeable with a sublimable dye.

Inventors: KOMETANI SHINJI, SAITO HITOSHI, TAKAO SHINO, KOMETANI, SHINJI, SAITO, HITOSHI, TAKAO, SHINO
Applicants: DAINIPPON PRINTING CO LTD, DAI NIPPON PRINTING CO., LTD.
Application year: 1994
Main classification: B41M5
IPC codes: B41M5